CN1321117C - Thiadiazole compound and use thereof - Google Patents

Thiadiazole compound and use thereof Download PDF

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CN1321117C
CN1321117C CNB2003801012453A CN200380101245A CN1321117C CN 1321117 C CN1321117 C CN 1321117C CN B2003801012453 A CNB2003801012453 A CN B2003801012453A CN 200380101245 A CN200380101245 A CN 200380101245A CN 1321117 C CN1321117 C CN 1321117C
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ethyl
phenyl
methylol
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benzyl
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CN1703413A (en
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井原秀树
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/08—1,2,4-Thiadiazoles; Hydrogenated 1,2,4-thiadiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

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  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)

Abstract

A thiadiazole compound represented by the formula (A): (A) wherein R<1> represents C1-7 alkyl, C3-7 alkenyl, C3-7 alkynyl, etc.; and R<2> represents C1-4 alkyl substituted by an optionally substituted heterocyclic group (provided that the heterocycle is a five-membered ring containing one or more oxygen or sulfur atoms as the only heteroatom(s)). The compound is highly active in controlling harmful arthropods.

Description

Thiadiazole compound and uses thereof
Invention field
The present invention relates to a kind of thiadiazole compound and uses thereof.
Background technology
The known a kind of effective constituent (DE3030661 announcement) that has a kind of thiadiazole compound can be used as arthropod control combination thing.
But the arthropod of this thiadiazole compound control activity is insufficient sometimes, therefore needs to have stronger arthropod and control active new compound.
Summary of the invention
Through contriver's conscientiously research, found that the thiadiazole compound shown in the following molecular formula (A) has excellent arthropod control activity, thereby finished the present invention.
That is, the present invention relates to the thiadiazole compound shown in a kind of molecular formula (A) (being called compound of the present invention later on):
Wherein, the R in the molecular formula 1Represent the C1-C7 alkyl, C3-C7 alkenyl, C3-C7 alkynyl, the C2-C7 alkoxyalkyl, C2-C7 alkane sulfane base, C4-C7 alcoxyl alkoxyalkyl, C4-C7 alkane sulfane oxyalkyl can substituted phenyl, the C1-C2 alkyl that is replaced by phenyl, wherein phenyl can be substituted, by the C1-C2 alkyl that phenoxy group replaces, wherein phenoxy group can be substituted, the C2-C3 alkoxyalkyl that is replaced by phenyl, wherein phenyl can be substituted, perhaps the group shown in the general formula (B):
Figure C20038010124500051
R wherein 3Represent the C1-C3 alkyl, R 4Represent hydrogen atom, methyl, ethyl, propyl group or phenyl, wherein phenyl can be substituted; And R 2The C1-C4 alkyl that representative is replaced by heterocyclic radical, wherein heterocyclic radical can be substituted, and described heterocyclic radical is only to contain Sauerstoffatom or sulphur atom as heteroatomic five-ring; The invention still further relates to the arthropod control combination thing of The compounds of this invention as activeconstituents, and a kind of method of controlling arthropod, this method comprises the The compounds of this invention of using significant quantity to arthropod or its habitat.
In the compound of the present invention, R 1Or R 2Each shown substituting group specific examples is as follows.
R 1The C1-C7 alkyl of representative comprises, for example methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl and the tertiary butyl.
R 1The C3-C7 alkenyl of representative comprises, for example allyl group, crotyl, 3-methyl-2-butene base and pentenyl.
R 1The C3-C7 alkynyl of representative comprises, for example 2-propynyl, 1-methyl-2-propynyl, 2-butyne base, 3-butynyl and valerylene base.
R 1The C2-C7 alkoxyalkyl of representative comprises, (C1-C6 alcoxyl) methyl for example; More specifically be methoxyl methyl, ethoxymethyl, the third oxygen methyl and the different third oxygen methyl.
R 1The C2-C7 alkane sulfane base of representative comprises, (C1-C6 alkane sulphur) alkyl for example; More specifically be first thiomethyl, second thiomethyl, rosickyite methyl and iprotiazem methyl.
R 1The C4-C7 alcoxyl alkoxyalkyl of representative comprises, methoxy (ethoxy) methyl for example.
R 1The C4-C7 alkane sulfane oxyalkyl of representative comprises, second sulphur ethoxymethyl for example.
R 1The phenyl of representative, wherein phenyl can be substituted, comprise, the phenyl that for example can be selected replaces from one or more substituting groups of following group: C1-C4 alkyl (methyl, ethyl, propyl group, sec.-propyl, the tertiary butyl etc.), C1-C4 haloalkyl (trifluoromethyl, difluoromethyl, pentafluoroethyl group etc.), C1-C4 alkoxyl group (methoxyl group, oxyethyl group, propoxy-, isopropoxy etc.), C1-C4 alkylthio (methylthio group, ethylmercapto group etc.), C1-C2 halogenated alkoxy (trifluoromethoxy, difluoro-methoxy etc.), nitro, cyano group and halogen atom (fluorine atom, the chlorine atom, bromine atoms etc.); Phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl are more specifically arranged, the 4-aminomethyl phenyl, 2-trifluoromethyl, 3-trifluoromethyl, 4-trifluoromethyl, the 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-methylthio group phenyl, 3-methylthio group phenyl, 4-methylthio group phenyl, 2-trifluoromethoxy benzaldehyde base, 3-trifluoromethoxy benzaldehyde base, 4-trifluoromethoxy benzaldehyde base, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, the 2-cyano-phenyl, 3-cyano-phenyl, 4-cyano-phenyl, 2-fluorophenyl, the 3-fluorophenyl, 4-fluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2,6-difluorophenyl, the 2,4 difluorobenzene base, 2-chloro-phenyl-, 3-chloro-phenyl-, the 4-chloro-phenyl-, 3,4-dichlorophenyl, 3, the 5-dichlorophenyl, 2,6-dichlorophenyl, 2, the 4-dichlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 3,4-dibromo phenyl, 3,5-dibromo phenyl, 2,6-dibromo phenyl and 2,4-dibromo phenyl.
R 1The C1-C2 alkyl that is replaced by phenyl (wherein phenyl can be substituted) of representative comprises, the C1-C2 alkyl that is replaced by phenyl for example, wherein phenyl can replace by selected one or more substituting group from following group: C1-C4 alkyl (methyl, ethyl, propyl group, sec.-propyl, the tertiary butyl etc.), C1-C4 haloalkyl (trifluoromethyl, difluoromethyl, pentafluoroethyl group etc.), C1-C4 alkoxyl group (methoxyl group, oxyethyl group, propoxy-, isopropoxy etc.), C1-C4 alkylthio (methylthio group, ethylmercapto group etc.), C1-C2 halogenated alkoxy (trifluoromethoxy, difluoro-methoxy etc.), nitro, cyano group and halogen atom (fluorine atom, the chlorine atom, bromine atoms etc.); Benzyl, 2-methyl-benzyl are more specifically arranged, the 3-methyl-benzyl, 4-methyl-benzyl, 2-trifluoromethyl benzyl, the 3-trifluoromethyl benzyl, 4-trifluoromethyl benzyl, 2-methoxybenzyl, the 3-methoxybenzyl, 4-methoxybenzyl, 2-methylthio group benzyl, 3-methylthio group benzyl, 4-methylthio group benzyl, 2-trifluoro methoxybenzyl, 3-trifluoro methoxybenzyl, 4-trifluoro methoxybenzyl, 2-nitrobenzyl, the 3-nitrobenzyl, 4-nitrobenzyl, 2-cyano group benzyl, 3-cyano group benzyl, 4-cyano group benzyl, 2-luorobenzyl, the 3-luorobenzyl, 4-luorobenzyl, 3, the 4-difluorobenzyl, 3, the 5-difluorobenzyl, 2,6-difluorobenzyl, 2, the 4-difluorobenzyl, 2-benzyl chloride base, 3-benzyl chloride base, 4-benzyl chloride base, 3, the 4-dichloro benzyl, 3,5-dichloro benzyl, 2, the 6-dichloro benzyl, 2, the 4-dichloro benzyl, the 2-bromobenzyl, 3-bromobenzyl, 4-bromobenzyl, 3,4-dibromo-benzyl, 3, the 5-dibromo-benzyl, 2, the 6-dibromo-benzyl, 2,4-dibromo-benzyl, 1-phenylethyl, 1-(2-aminomethyl phenyl) ethyl, 1-(3-aminomethyl phenyl) ethyl, 1-(4-aminomethyl phenyl) ethyl, 1-(2-trifluoromethyl) ethyl, 1-(3-trifluoromethyl) ethyl, 1-(4-trifluoromethyl) ethyl, 1-(2-methoxyphenyl) ethyl, 1-(3-methoxyphenyl) ethyl, 1-(4-methoxyphenyl) ethyl, 1-(2-methylthio group phenyl) ethyl, 1-(3-methylthio group phenyl) ethyl, 1-(4-methylthio group phenyl) ethyl, 1-(2-trifluoromethoxy benzaldehyde base) ethyl, 1-(3-trifluoromethoxy benzaldehyde base) ethyl, 1-(4-trifluoromethoxy benzaldehyde base) ethyl, 1-(2-nitrophenyl) ethyl, 1-(3-nitrophenyl) ethyl, 1-(4-nitrophenyl) ethyl, 1-(2-cyano-phenyl) ethyl, 1-(3-cyano-phenyl) ethyl, 1-(4-cyano-phenyl) ethyl, 1-(2-fluorophenyl) ethyl, 1-(3-fluorophenyl) ethyl, 1-(4-fluorophenyl) ethyl, 1-(3, the 4-difluorophenyl) ethyl, 1-(3, the 5-difluorophenyl) ethyl, 1-(2, the 6-difluorophenyl) ethyl, 1-(2,4 difluorobenzene base) ethyl, 1-(2-chloro-phenyl-) ethyl, 1-(3-chloro-phenyl-) ethyl, 1-(4-chloro-phenyl-) ethyl, 1-(3, the 4-dichlorophenyl) ethyl, 1-(3, the 5-dichlorophenyl) ethyl, 1-(2, the 6-dichlorophenyl) ethyl, 1-(2, the 4-dichlorophenyl) ethyl, 1-(2-bromophenyl) ethyl, 1-(3-bromophenyl) ethyl, 1-(4-bromophenyl) ethyl, 1-(3, the 4-dibromo phenyl) ethyl, 1-(3, the 5-dibromo phenyl) ethyl, 1-(2, the 6-dibromo phenyl) ethyl, 1-(2, the 4-dibromo phenyl) ethyl, the 2-phenylethyl, 2-(2-aminomethyl phenyl) ethyl, 2-(3-aminomethyl phenyl) ethyl, 2-(4-aminomethyl phenyl) ethyl, 2-(2-trifluoromethyl) ethyl, 2-(3-trifluoromethyl) ethyl, 2-(4-trifluoromethyl) ethyl, 2-(2-methoxyphenyl) ethyl, 2-(3-methoxyphenyl) ethyl, 2-(4-methoxyphenyl) ethyl, 2-(2-methylthio group phenyl) ethyl, 2-(3-methylthio group phenyl) ethyl, 2-(4-methylthio group phenyl) ethyl, 2-(2-trifluoromethoxy benzaldehyde base) ethyl, 2-(3-trifluoromethoxy benzaldehyde base) ethyl, 2-(4-trifluoromethoxy benzaldehyde base) ethyl, 2-(2-nitrophenyl) ethyl, 2-(3-nitrophenyl) ethyl, 2-(4-nitrophenyl) ethyl, 2-(2-cyano-phenyl) ethyl, 2-(3-cyano-phenyl) ethyl, 2-(4-cyano-phenyl) ethyl, 2-(2-fluorophenyl) ethyl, 2-(3-fluorophenyl) ethyl, 2-(4-fluorophenyl) ethyl, 2-(3, the 4-difluorophenyl) ethyl, 2-(3, the 5-difluorophenyl) ethyl, 2-(2, the 6-difluorophenyl) ethyl, 2-(2, the 4-difluorophenyl) ethyl, 2-(2-chloro-phenyl-) ethyl, 2-(3-chloro-phenyl-) ethyl, 2-(4-chloro-phenyl-) ethyl, 2-(3, the 4-dichlorophenyl) ethyl, 2-(3, the 5-dichlorophenyl) ethyl, 2-(2, the 6-dichlorophenyl) ethyl, 2-(2, the 4-dichlorophenyl) ethyl, 2-(2-bromophenyl) ethyl, 2-(3-bromophenyl) ethyl, 2-(4-bromophenyl) ethyl, 2-(3, the 4-dibromo phenyl) ethyl, 2-(3, the 5-dibromo phenyl) ethyl, 2-(2, the 6-dibromo phenyl) ethyl, 2-(2, the 4-dibromo phenyl) ethyl.
R 1The C1-C2 alkyl that is replaced by phenoxy group (wherein phenoxy group can be substituted) of representative comprises, the C1-C2 alkyl that is replaced by phenoxy group for example, wherein phenoxy group can replace by selected one or more substituting group from following group: C1-C4 alkyl (methyl, ethyl, propyl group, sec.-propyl, the tertiary butyl etc.), C1-C4 haloalkyl (trifluoromethyl, difluoromethyl, pentafluoroethyl group etc.), C1-C4 alkoxyl group (methoxyl group, oxyethyl group, propoxy-, isopropoxy etc.), C1-C4 alkylthio (methylthio group, ethylmercapto group etc.), C1-C2 halogenated alkoxy (trifluoromethoxy, difluoro-methoxy etc.), nitro, cyano group and halogen atom (fluorine atom, the chlorine atom, bromine atoms etc.); Phenoxymethyl is more specifically arranged, 1-(benzene oxygen) ethyl, 2-(benzene oxygen) ethyl, (2-aminomethyl phenyl) methylol, (3-aminomethyl phenyl) methylol, (4-aminomethyl phenyl) methylol, (2-trifluoromethyl) methylol, (3-trifluoromethyl) methylol, (4-trifluoromethyl) methylol, (2-methoxyphenyl) methylol, (3-methoxyphenyl) methylol, (4-methoxyphenyl) methylol, (2-methylthio group phenyl) methylol, (3-methylthio group phenyl) methylol, (4-methylthio group phenyl) methylol, (2-trifluoromethoxy benzaldehyde base) methylol, (3-trifluoromethoxy benzaldehyde base) methylol, (4-trifluoromethoxy benzaldehyde base) methylol, (2-nitrophenyl) methylol, (3-nitrophenyl) methylol, (4-nitrophenyl) methylol, (2-cyano-phenyl) methylol, (3-cyano-phenyl) methylol, (4-cyano-phenyl) methylol, (2-fluorophenyl) methylol, (3-fluorophenyl) methylol, (4-fluorophenyl) methylol, (3, the 4-difluorophenyl) methylol, (3, the 5-difluorophenyl) methylol, (2,6 difluorophenyls) methylol, (2,4 difluorobenzene base) methylol, (2-chloro-phenyl-) methylol, (3-chloro-phenyl-) methylol, (4-chloro-phenyl-) methylol, (3, the 4-dichlorophenyl) methylol, (3, the 5-dichlorophenyl) methylol, (2, the 6-dichlorophenyl) methylol, (2, the 4-dichlorophenyl) methylol, (2-bromophenyl) methylol, (3-bromophenyl) methylol, (4-bromophenyl) methylol, (3, the 4-dibromo phenyl) methylol, (3, the 5-dibromo phenyl) methylol, (2, the 6-dibromo phenyl) methylol and (2, the 4-dibromo phenyl) methylol.
R 1The C2-C3 alkoxyalkyl that is replaced by phenyl (wherein phenyl can be substituted) of representative comprises, the methoxyl methyl that is replaced by phenyl for example, wherein phenyl can replace by selected one or more substituting group from following group: C1-C4 alkyl (methyl, ethyl, propyl group, sec.-propyl, the tertiary butyl etc.), C1-C4 haloalkyl (trifluoromethyl, difluoromethyl, pentafluoroethyl group etc.), C1-C4 alkoxyl group (methoxyl group, oxyethyl group, propoxy-, isopropoxy etc.), C1-C4 alkylthio (methylthio group, ethylmercapto group etc.), C1-C2 halogenated alkoxy (trifluoromethoxy, difluoro-methoxy etc.), nitro, cyano group and halogen atom (fluorine atom, the chlorine atom, bromine atoms etc.); Benzyloxymethyl is more specifically arranged, (2-methyl-benzyl) methylol, (3-methyl-benzyl) methylol, (4-methyl-benzyl) methylol, (2-trifluoromethyl benzyl) methylol, (3-trifluoromethyl benzyl) methylol, (4-trifluoromethyl benzyl) methylol, (2-methoxybenzyl) methylol, (3-methoxybenzyl) methylol, (4-methoxybenzyl) methylol, (2-methylthio group benzyl) methylol, (3-methylthio group benzyl) methylol, (4-methylthio group benzyl) methylol, (2-trifluoro methoxybenzyl) methylol, (3-trifluoro methoxybenzyl) methylol, (4-trifluoro methoxybenzyl) methylol, (2-nitrobenzyl) methylol, (3-nitrobenzyl) methylol, (4-nitrobenzyl) methylol, (2-cyano group benzyl) methylol, (3-cyano group benzyl) methylol, (4-cyano group benzyl) methylol, (2-luorobenzyl) methylol, (3-luorobenzyl) methylol, (4-luorobenzyl) methylol, (3, the 4-difluorobenzyl) methylol, (3, the 5-difluorobenzyl) methylol, (2, the 6-difluorobenzyl) methylol, (2, the 4-difluorobenzyl) methylol, (2-benzyl chloride base) methylol, (3-benzyl chloride base) methylol, (4-benzyl chloride base) methylol, (3, the 4-dichloro benzyl) methylol, (3, the 5-dichloro benzyl) methylol, (2, the 6-dichloro benzyl) methylol, (2, the 4-dichloro benzyl) methylol, (2-bromobenzyl) methylol, (3-bromobenzyl) methylol, (4-bromobenzyl) methylol, (3, the 4-dibromo-benzyl) methylol, (3, the 5-dibromo-benzyl) methylol, (2, the 6-dibromo-benzyl) methylol and (2, the 4-dibromo-benzyl) methylol.
R 1The general formula (B) of representative comprises, R for example 3Be the C1-C3 alkyl, R 4Be hydrogen atom or phenyl, wherein phenyl can replace by selected one or more substituting group from following group: C1-C4 alkyl (methyl, ethyl, propyl group, sec.-propyl, the tertiary butyl etc.), C1-C4 haloalkyl (trifluoromethyl, difluoromethyl, pentafluoroethyl group etc.), C1-C4 alkoxyl group (methoxyl group, oxyethyl group, propoxy-, isopropoxy etc.), C1-C4 alkylthio (methylthio group, ethylmercapto group etc.), C1-C2 halogenated alkoxy (trifluoromethoxy, difluoro-methoxy etc.), nitro, cyano group and halogen atom (fluorine atom, chlorine atom, bromine atoms etc.); Acetoxyl methyl and α-acetoxyl group benzyl is more specifically arranged.
R 2The C1-C4 alkyl that representative is replaced by heterocyclic radical (later on this heterocyclic radical being called heterocyclic radical of the present invention), wherein heterocyclic radical can be substituted, and this heterocyclic radical is only to contain Sauerstoffatom or sulphur atom as heteroatomic five-ring, R 2Shown in group comprise, the C1-C4 alkyl that is replaced by heterocyclic radical of the present invention for example, heterocyclic radical wherein of the present invention can replace by selected one or more substituting group from following group: C1-C4 alkyl (methyl, ethyl, propyl group, sec.-propyl, the tertiary butyl etc.), halogen atom (fluorine atom, chlorine atom, bromine atoms etc.), trifluoromethyl, formyl radical and nitro; More specifically; the methyl that is replaced by heterocyclic radical of the present invention; heterocyclic radical wherein of the present invention can replace by selected one or more substituting group from following group: halogen atom (fluorine atom; the chlorine atom; bromine atoms etc.); C1-C4 alkyl (methyl; ethyl; propyl group; sec.-propyl; the tertiary butyl etc.); trifluoromethyl; formyl radical and nitro; and the ethyl that on ethyl 1-position, contains heterocyclic radical of the present invention; heterocyclic radical wherein of the present invention can replace by selected one or more substituting group from following group: C1-C4 alkyl (methyl; ethyl; propyl group; sec.-propyl; the tertiary butyl etc.); halogen atom (fluorine atom; the chlorine atom; bromine atoms etc.); trifluoromethyl, formyl radical and nitro.
At R 2In the C1-C4 alkyl that is replaced by heterocyclic radical of the present invention of representative, heterocyclic radical of the present invention comprises, for example only contain Sauerstoffatom as heteroatomic five-ring, only contain Sauerstoffatom as heteroatomic saturated five-ring, only contain two Sauerstoffatoms as heteroatomic saturated five-ring, only contain a Sauerstoffatom as heteroatomic five-ring, a sulfur atom-containing is as heteroatomic five-ring.
R 2The C1-C4 alkyl pattern that is replaced by heterocyclic radical of the present invention (heterocyclic radical wherein of the present invention can be substituted) of representative comprises for example following general formula (1)-(10) described group.
General formula (1):
Figure C20038010124500101
R in its Chinese style 10Represent hydrogen atom or methyl, R 11Represent halogen atom, C1-C4 alkyl, trifluoromethyl, formyl radical or nitro, X 1Represention oxygen atom or sulphur atom, m are 1 or 2, and n represents the integer of 0-3.When n is during more than or equal to 2 integer, each R 11Can be the same or different;
General formula (2):
R in its Chinese style 10Represent hydrogen atom or methyl, R 12Represent the C1-C4 alkyl, X 1Represention oxygen atom or sulphur atom, m are 1 or 2, and p represents the integer of 0-7.When p is during more than or equal to 2 integer, each R 12Can be the same or different;
General formula (3):
Figure C20038010124500103
R in its Chinese style 10Represent hydrogen atom or methyl, R 13Represent the C1-C4 alkyl, X 1Represention oxygen atom or sulphur atom, m are 1 or 2, and q represents the integer of 0-5.When q is during more than or equal to 2 integer, each R 13Can be the same or different;
General formula (4):
Figure C20038010124500104
R in its Chinese style 11Represent halogen atom, C1-C4 alkyl, trifluoromethyl, formyl radical or nitro, n represents the integer of 0-3.When n is during more than or equal to 2 integer, each R 11Can be the same or different;
General formula (5):
Figure C20038010124500111
R in its Chinese style 11Represent halogen atom, C1-C4 alkyl, trifluoromethyl, formyl radical or nitro, n represents the integer of 0-3.When n is during more than or equal to 2 integer, each R 11Can be the same or different;
General formula (6):
Figure C20038010124500112
R in its Chinese style 12Represent the C1-C4 alkyl, p represents the integer of 0-7.When p is during more than or equal to 2 integer, each R 12Can be the same or different;
General formula (7):
Figure C20038010124500113
R in its Chinese style 12Represent the C1-C4 alkyl, p represents the integer of 0-7.When p is during more than or equal to 2 integer, each R 12Can be the same or different;
General formula (8):
Figure C20038010124500114
R in its Chinese style 13Represent the C1-C4 alkyl, q represents the integer of 0-5.When q is during more than or equal to 2 integer, each R 13Can be the same or different;
General formula (9):
Figure C20038010124500121
R in its Chinese style 13Represent the C1-C4 alkyl, q represents the integer of 0-5.When q is during more than or equal to 2 integer, each R 13Can be the same or different;
General formula (10):
Figure C20038010124500122
R in its Chinese style 13Represent the C1-C4 alkyl, two R 13Can be the same or different each other.
Concrete The compounds of this invention comprises, for example following compound:
The thiadiazole compound of formula (A), wherein R 1It is the C1-C7 alkyl;
The thiadiazole compound of formula (A), wherein R 1Be C3-C7 alkenyl, C2-C7 alkoxyalkyl, C2-C7 alkane sulfane base, C4-C7 alcoxyl alkoxyalkyl or C4-C7 alkane sulfane oxyalkyl; The thiadiazole compound of formula (A), wherein R 1Be phenyl, wherein phenyl can replace by selected one or more substituting groups from substituent A; By the C1-C2 alkyl that phenyl replaces, wherein phenyl can replace by selected one or more substituting groups from substituent A; By the C1-C2 alkyl that phenoxy group replaces, wherein phenoxy group can replace by selected one or more substituting groups from substituent A; The perhaps C2-C3 alkoxyalkyl that is replaced by phenyl, wherein phenyl can replace by selected one or more substituting groups from substituent A,
Substituent A
C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxyl group, C1-C4 alkylthio, C1-C4 halogenated alkoxy, nitro, cyano group and halogen atom;
Thiadiazole compound in the formula (A), wherein R 1Be the represented group of general formula (B):
R in its Chinese style 3Represent the C1-C3 alkyl, R 4Represent hydrogen atom, methyl, ethyl, the optional phenyl that replaces of perhaps selected one or more substituting groups: C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxyl group, C1-C4 alkylthio, C1-C2 halogenated alkoxy, nitro, cyano group and halogen atom from following group;
Thiadiazole compound in the formula (A), wherein R 1Be the optional phenyl that replace of selected one or more substituting groups from substituent A, the optional benzyl that replaces of selected one or more substituting groups from substituent A, optional Phenoxymethyl that replaces of selected one or more substituting groups or the selected optional benzyloxymethyl that replaces of one or more substituting groups from substituent A from substituent A;
Thiadiazole compound in the formula (A), wherein R 2Be the represented group of general formula (1):
R in the formula (1) 10Represent hydrogen atom or methyl, R 11Represent halogen atom, C1-C4 alkyl, trifluoromethyl, formyl radical or nitro, X 1Represention oxygen atom or sulphur atom, m represent 1 or 2, and n represents the integer of 0-3, when n is during more than or equal to 2 integer, and each R 11Can be the same or different the represented group of general formula (2):
Figure C20038010124500133
R in the formula (2) 10Represent hydrogen atom or methyl, R 12Represent the C1-C4 alkyl, X 1Represention oxygen atom or sulphur atom, m represent 1 or 2, and p represents the integer of 0-7, when p is during more than or equal to 2 integer, and each R 12Can be the same or different, perhaps
The represented group of general formula (3):
R in the formula (3) 10Represent hydrogen atom or methyl, R 13Represent the C1-C4 alkyl, X 1Represention oxygen atom or sulphur atom, m represent 1 or 2, and q represents the integer of 0-5, when q is during more than or equal to 2 integer, and each R 13Can be the same or different;
Thiadiazole compound, wherein R 1Be the represented group of general formula (4):
Figure C20038010124500142
R in the formula (4) 11Represent halogen atom, C1-C4 alkyl, trifluoromethyl, formyl radical or nitro, n represents the integer of 0-3, when n is during more than or equal to 2 integer, and each R 11Can be the same or different,
The represented group of general formula (5):
Figure C20038010124500143
R in the formula (5) 11Represent halogen atom, C1-C4 alkyl, trifluoromethyl, formyl radical or nitro, n represents the integer of 0-3, when n is during more than or equal to 2 integer, and each R 11Can be the same or different,
The represented group of general formula (6):
Figure C20038010124500144
R in the formula (6) 12Represent the C1-C4 alkyl, p represents the integer of 0-7, when p is during more than or equal to 2 integer, and each R 12Can be the same or different,
The represented group of general formula (7):
Figure C20038010124500151
R in the formula (7) 12Represent the C1-C4 alkyl, p represents the integer of 0-7, when p is during more than or equal to 2 integer, and each R 12Can be the same or different,
The represented group of general formula (8):
Figure C20038010124500152
R in the formula (8) 13Represent the C1-C4 alkyl, q represents the integer of 0-5, when q is during more than or equal to 2 integer, and each R 13Can be the same or different,
The represented group of general formula (9):
Figure C20038010124500153
R in the formula (9) 13Represent the C1-C4 alkyl, q represents the integer of 0-5, when q is during more than or equal to 2 integer, and each R 13Can be the same or different, perhaps
The represented group of general formula (10):
R in the formula (10) 13Represent the C1-C4 alkyl, two R 13Can be the same or different.
The preparation method of The compounds of this invention will be described below.
In compound of the present invention, R wherein 1Represent the compound of following group: the C1-C7 alkyl, the C3-C7 alkenyl, the C3-C7 alkynyl, the C2-C7 alkoxyalkyl, C2-C7 alkane sulfane base, C4-C7 alcoxyl alkoxyalkyl, C4-C7 alkane sulfane oxyalkyl, phenyl, wherein phenyl can be substituted, phenyl C1-C2 alkyl, wherein phenyl can be substituted, phenoxy group C1-C2 alkyl, wherein phenoxy group can be substituted, perhaps phenyl C2-C3 alkoxyalkyl, wherein phenyl can be substituted, it is the compound shown in the general formula (A-1), it can pass through for example with the 5-chloro-1 shown in the general formula (I), 2, alkylol cpd shown in 4-thiadiazole compound and the general formula (II) reacts and prepares
Figure C20038010124500161
The R in the following formula wherein 1-1Represent C1-C7 alkyl, C3-C7 alkenyl, C3-C7 alkynyl, C2-C7 alkoxyalkyl, C2-C7 alkane sulfane base, C4-C7 alcoxyl alkoxyalkyl, C4-C7 alkane sulfane oxyalkyl, phenyl, wherein phenyl can be substituted, phenyl C1-C2 alkyl, wherein phenyl can be substituted, phenoxy group C1-C2 alkyl, wherein phenoxy group can be substituted, perhaps phenyl C2-C3 alkoxyalkyl, wherein phenyl can be substituted; R 2Implication is the same.
Reaction generally is in the presence of alkali, carries out in solvent usually.
React used solvent and comprise, aliphatic hydrocarbon for example is as hexane, heptane, octane etc.; Aromatic hydrocarbons is as toluene, dimethylbenzene etc.; Ethers, as tetrahydrofuran (THF), 1,4-diox, methyl-tertbutyl ether, 1,2-glycol dimethyl ether etc.; N, dinethylformamide, and composition thereof.
React used alkali and comprise, carbonate for example, as salt of wormwood, yellow soda ash etc., and composition thereof.
Quantity as for the reaction agents useful for same, the consumption of the alkylol cpd shown in the general formula (II) is with respect to 5-chloro-1 shown in 1 mole of general formula (I), 2, the 4-thiadiazole compound is generally the 1-1.5 mole, and the consumption of alkali is the 1-1.5 mole with respect to alkylol cpd shown in the general formula (II).
Temperature of reaction is generally-20-80 ℃, and the reaction times is generally 0.5-24 hour.
After reaction is finished, can carry out aftertreatment to reaction mixture and isolate the The compounds of this invention shown in the general formula (A-1), for example reaction mixture is added in the water, use organic solvent extraction, dry and concentrated extract etc.If desired, can carry out purifying, the technology of employing such as chromatography, recrystallization etc. to the The compounds of this invention shown in the isolated general formula (A-1).
In the compound of the present invention, the R in compound 1Represent the group shown in the general formula (B), when being the compound shown in the general formula (A-2), can prepare with the following method, for example allow thiadiazole compound shown in the general formula (III) and oxidant reaction (be called later on before half step), then, with preceding half product and the anhydride reaction shown in the logical formula V (being called the later half step later on) that goes on foot.
Wherein, the R in the following formula 2, R 3And R 4As defined above.
(preceding half step)
Preceding half step reaction is generally carried out in solvent.React solvent for use and comprise, for example halogenated aliphatic hydrocarbon and water, halogenated aliphatic hydrocarbon such as methylene dichloride, chloroform etc.
The oxygenant that reaction is used comprises, peroxy acid for example is as 3-chlorine peroxybenzoic acid.The oxygenant quantity that reaction is used is generally the 1-1.5 mole with respect to thiadiazole compound shown in 1 mole of general formula (III).
Temperature of reaction is generally-20 ℃-30 ℃, and the reaction times is generally moment-24 hour.
After reaction is finished, can carry out aftertreatment to reaction mixture and isolate the sulfoxide compound shown in the general formula (IV), for example reaction mixture is added in the water; Use organic solvent extraction; If necessary, with reductive agent (for example S-WAT, the Sulfothiorine etc.) aqueous solution, the organic layer that the solution washing of alkali (sodium bicarbonate etc.) obtains; Dry and concentrated organic layer etc.Can carry out purifying, the technology of employing such as chromatography, recrystallization etc. to the sulfoxide compound shown in the isolated general formula (IV).
(later half step)
The later half step can carry out like this: allow the anhydride reaction shown in sulfoxide compound shown in the general formula (IV) and the logical formula V.
Reaction can be carried out in solvent, also can not have solvent, normally reacts in the presence of alkali.
React used alkali and comprise, pyridine for example, such as 2,6-lutidine etc.; Alkali metal acetate is as sodium acetate etc.
As for the quantity of reaction agents useful for same, for the sulfoxide compound shown in every mole of general formula (IV), the consumption of acid anhydrides is the 1-50 mole shown in the logical formula V, and the consumption of alkali is the 1-10 mole.
If desired, reaction can be carried out in the presence of trifluoroacetic anhydride.In this case, the trifluoroacetic anhydride consumption of sulfoxide compound is generally the 0.01-5 mole shown in every mole of general formula (IV).
Temperature of reaction is generally 0-150 ℃, and the reaction times is generally 1-72 hour.
After reaction is finished, can carry out aftertreatment to reaction mixture, isolate the The compounds of this invention shown in the general formula (A-2), for example reaction mixture is added in the aqueous solution of alkali (for example sodium bicarbonate), use organic solvent extraction, dry and concentrated gained organic layer etc.If desired, can carry out purifying, the technology of employing such as chromatography, recrystallization etc. to the The compounds of this invention shown in the isolated general formula (A-2).
Can adopt for example Chem.Ber.90, the method described in 892 (1957) prepares the compound shown in the general formula (I).
What show below is the example of The compounds of this invention.
Figure C20038010124500201
Figure C20038010124500211
In general formula (i)-(xx), R 1Representative is selected from a group of following group: methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, the tertiary butyl, allyl group, crotyl, 3-methyl-2-butene base, pentenyl, 2-propynyl, 1-methyl-2-propynyl, the 2-butyne base, the 3-butynyl, the valerylene base, methoxyl methyl, ethoxymethyl, the third oxygen methyl, the different third oxygen methyl, fourth oxygen methyl, isobutyl oxygen methyl, Zhong Ding oxygen methyl, uncle's fourth oxygen methyl, the first thiomethyl, the second thiomethyl, the rosickyite methyl, the iprotiazem methyl, the methoxy (ethoxy) methyl, the ethoxy ethoxymethyl, first sulphur ethoxymethyl, phenyl, the 2-aminomethyl phenyl, the 3-aminomethyl phenyl, the 4-aminomethyl phenyl, the 2-trifluoromethyl, the 3-trifluoromethyl, the 4-trifluoromethyl, the 2-methoxyphenyl, the 3-methoxyphenyl, the 4-methoxyphenyl, 2-methylthio group phenyl, 3-methylthio group phenyl, 4-methylthio group phenyl, 2-trifluoromethoxy benzaldehyde base, 3-trifluoromethoxy benzaldehyde base, 4-trifluoromethoxy benzaldehyde base, the 2-nitrophenyl, the 3-nitrophenyl, the 4-nitrophenyl, the 2-cyano-phenyl, the 3-cyano-phenyl, the 4-cyano-phenyl, the 2-fluorophenyl, the 3-fluorophenyl, the 4-fluorophenyl, 3, the 4-difluorophenyl, 3, the 5-difluorophenyl, 2, the 6-difluorophenyl, 2, the 4-difluorophenyl, the 2-chloro-phenyl-, the 3-chloro-phenyl-, the 4-chloro-phenyl-, 3, the 4-dichlorophenyl, 3, the 5-dichlorophenyl, 2, the 6-dichlorophenyl, 2, the 4-dichlorophenyl, the 2-bromophenyl, the 3-bromophenyl, the 4-bromophenyl, 3, the 4-dibromo phenyl, 3, the 5-dibromo phenyl, 2, the 6-dibromo phenyl, 2, the 4-dibromo phenyl, benzyl, the 2-methyl-benzyl, the 3-methyl-benzyl, the 4-methyl-benzyl;
The 2-trifluoromethyl benzyl, the 3-trifluoromethyl benzyl, the 4-trifluoromethyl benzyl, the 2-methoxybenzyl, the 3-methoxybenzyl, the 4-methoxybenzyl, 2-methylthio group benzyl, 3-methylthio group benzyl, 4-methylthio group benzyl, 2-trifluoro methoxybenzyl, 3-trifluoro methoxybenzyl, 4-trifluoro methoxybenzyl, the 2-nitrobenzyl, the 3-nitrobenzyl, the 4-nitrobenzyl, 2-cyano group benzyl, 3-cyano group benzyl, 4-cyano group benzyl, the 2-luorobenzyl, the 3-luorobenzyl, the 4-luorobenzyl, 3, the 4-difluorobenzyl, 3, the 5-difluorobenzyl, 2, the 6-difluorobenzyl, 2, the 4-difluorobenzyl, 2-benzyl chloride base, 3-benzyl chloride base, 4-benzyl chloride base, 3, the 4-dichloro benzyl, 3, the 5-dichloro benzyl, 2, the 6-dichloro benzyl, 2, the 4-dichloro benzyl, the 2-bromobenzyl, the 3-bromobenzyl, the 4-bromobenzyl, 3, the 4-dibromo-benzyl, 3, the 5-dibromo-benzyl, 2, the 6-dibromo-benzyl, 2, the 4-dibromo-benzyl, the 1-phenylethyl, 1-(2-aminomethyl phenyl) ethyl, 1-(3-aminomethyl phenyl) ethyl, 1-(4-aminomethyl phenyl) ethyl, 1-(2-trifluoromethyl) ethyl, 1-(3-trifluoromethyl) ethyl, 1-(4-trifluoromethyl) ethyl, 1-(2-methoxyphenyl) ethyl, 1-(3-methoxyphenyl) ethyl, 1-(4-methoxyphenyl) ethyl, 1-(2-methylthio group phenyl) ethyl, 1-(3-methylthio group phenyl) ethyl, 1-(4-methylthio group phenyl) ethyl, 1-(2-trifluoromethoxy benzaldehyde base) ethyl, 1-(3-trifluoromethoxy benzaldehyde base) ethyl, 1-(4-trifluoromethoxy benzaldehyde base) ethyl, 1-(2-nitrophenyl) ethyl, 1-(3-nitrophenyl) ethyl, 1-(4-nitrophenyl) ethyl, 1-(2-cyano-phenyl) ethyl, 1-(3-cyano-phenyl) ethyl, 1-(4-cyano-phenyl) ethyl, 1-(2-fluorophenyl) ethyl, 1-(3-fluorophenyl) ethyl, 1-(4-fluorophenyl) ethyl, 1-(3, the 4-difluorophenyl) ethyl, 1-(3, the 5-difluorophenyl) ethyl, 1-(2, the 6-difluorophenyl) ethyl, 1-(2, the 4-difluorophenyl) ethyl, 1-(2-chloro-phenyl-) ethyl, 1-(3-chloro-phenyl-) ethyl, 1-(4-chloro-phenyl-) ethyl, 1-(3, the 4-dichlorophenyl) ethyl, 1-(3, the 5-dichlorophenyl) ethyl, 1-(2, the 6-dichlorophenyl) ethyl, 1-(2, the 4-dichlorophenyl) ethyl, 1-(2-bromophenyl) ethyl, 1-(3-bromophenyl) ethyl, 1-(4-bromophenyl) ethyl, 1-(3, the 4-dibromo phenyl) ethyl, 1-(3, the 5-dibromo phenyl) ethyl, 1-(2, the 6-dibromo phenyl) ethyl, 1-(2, the 4-dibromo phenyl) ethyl, the 2-phenylethyl, 2-(2-aminomethyl phenyl) ethyl, 2-(3-aminomethyl phenyl) ethyl, 2-(4-aminomethyl phenyl) ethyl, 2-(2-trifluoromethyl) ethyl, 2-(3-trifluoromethyl) ethyl, 2-(4-trifluoromethyl) ethyl, 2-(2-methoxyphenyl) ethyl, 2-(3-methoxyphenyl) ethyl, 2-(4-methoxyphenyl) ethyl, 2-(2-methylthio group phenyl) ethyl, 2-(3-methylthio group phenyl) ethyl, 2-(4-methylthio group phenyl) ethyl, 2-(2-trifluoromethoxy benzaldehyde base) ethyl, 2-(3-trifluoromethoxy benzaldehyde base) ethyl, 2-(4-trifluoromethoxy benzaldehyde base) ethyl, 2-(2-nitrophenyl) ethyl, 2-(3-nitrophenyl) ethyl, 2-(4-nitrophenyl) ethyl, 2-(2-cyano-phenyl) ethyl, 2-(3-cyano-phenyl) ethyl, 2-(4-cyano-phenyl) ethyl, 2-(2-fluorophenyl) ethyl, 2-(3-fluorophenyl) ethyl, 2-(4-fluorophenyl) ethyl, 2-(3, the 4-difluorophenyl) ethyl, 2-(3, the 5-difluorophenyl) ethyl, 2-(2, the 6-difluorophenyl) ethyl, 2-(2, the 4-difluorophenyl) ethyl, 2-(2-chloro-phenyl-) ethyl, 2-(3-chloro-phenyl-) ethyl, 2-(4-chloro-phenyl-) ethyl, 2-(3, the 4-dichlorophenyl) ethyl, 2-(3, the 5-dichlorophenyl) ethyl, 2-(2, the 6-dichlorophenyl) ethyl, 2-(2, the 4-dichlorophenyl) ethyl, 2-(2-bromophenyl) ethyl, 2-(3-bromophenyl) ethyl, 2-(4-bromophenyl) ethyl, 2-(3, the 4-dibromo phenyl) ethyl, 2-(3, the 5-dibromo phenyl) ethyl, 2-(2, the 6-dibromo phenyl) ethyl, 2-(2, the 4-dibromo phenyl) ethyl, Phenoxymethyl, 1-(benzene oxygen) ethyl, 2-(benzene oxygen) ethyl, (2-aminomethyl phenyl) methylol, (3-aminomethyl phenyl) methylol, (4-aminomethyl phenyl) methylol, (2-trifluoromethyl) methylol, (3-trifluoromethyl) methylol, (4-trifluoromethyl) methylol, (2-methoxyphenyl) methylol, (3-methoxyphenyl) methylol, (4-methoxyphenyl) methylol, (2-methylthio group phenyl) methylol, (3-methylthio group phenyl) methylol, (4-methylthio group phenyl) methylol, (2-trifluoromethoxy benzaldehyde base) methylol, (3-trifluoromethoxy benzaldehyde base) methylol, (4-trifluoromethoxy benzaldehyde base) methylol, (2-nitrophenyl) methylol, (3-nitrophenyl) methylol, (4-nitrophenyl) methylol, (2-cyano-phenyl) methylol, (3-cyano-phenyl) methylol, (4-cyano-phenyl) methylol, (2-fluorophenyl) methylol, (3-fluorophenyl) methylol, (4-fluorophenyl) methylol, (3, the 4-difluorophenyl) methylol, (3, the 5-difluorophenyl) methylol, (2, the 6-difluorophenyl) methylol, (2, the 4-difluorophenyl) methylol, (2-chloro-phenyl-) methylol, (3-chloro-phenyl-) methylol, (4-chloro-phenyl-) methylol, (3, the 4-dichlorophenyl) methylol, (3, the 5-dichlorophenyl) methylol, (2, the 6-dichlorophenyl) methylol, (2, the 4-dichlorophenyl) methylol, (2-bromophenyl) methylol, (3-bromophenyl) methylol, (4-bromophenyl) methylol, (3, the 4-dibromo phenyl) methylol, (3, the 5-dibromo phenyl) methylol, (2, the 6-dibromo phenyl) methylol and (2, the 4-dibromo phenyl) methylol, benzyloxymethyl, (2-methyl-benzyl) methylol, (3-methyl-benzyl) methylol, (4-methyl-benzyl) methylol, (2-trifluoromethyl benzyl) methylol, (3-trifluoromethyl benzyl) methylol, (4-trifluoromethyl benzyl) methylol, (2-methoxybenzyl) methylol, (3-methoxybenzyl) methylol, (4-methoxybenzyl) methylol, (2-methylthio group benzyl) methylol, (3-methylthio group benzyl) methylol, (4-methylthio group benzyl) methylol, (2-trifluoro methoxybenzyl) methylol, (3-trifluoro methoxybenzyl) methylol, (4-trifluoro methoxybenzyl) methylol, (2-nitrobenzyl) methylol, (3-nitrobenzyl) methylol, (4-nitrobenzyl) methylol, (2-cyano group benzyl) methylol, (3-cyano group benzyl) methylol, (4-cyano group benzyl) methylol, (2-luorobenzyl) methylol, (3-luorobenzyl) methylol, (4-luorobenzyl) methylol, (3, the 4-difluorobenzyl) methylol, (3, the 5-difluorobenzyl) methylol, (2, the 6-difluorobenzyl) methylol, (2, the 4-difluorobenzyl) methylol, (2-benzyl chloride base) methylol, (3-benzyl chloride base) methylol, (4-benzyl chloride base) methylol, (3, the 4-dichloro benzyl) methylol, (3, the 5-dichloro benzyl) methylol, (2, the 6-dichloro benzyl) methylol, (2, the 4-dichloro benzyl) methylol, (2-bromobenzyl) methylol, (3-bromobenzyl) methylol, (4-bromobenzyl) methylol, (3, the 4-dibromo-benzyl) methylol, (3, the 5-dibromo-benzyl) methylol, (2, the 6-dibromo-benzyl) methylol and (2, the 4-dibromo-benzyl) methylol, the acetoxyl methyl, propionyloxy methyl and α-acetyl oxygen benzyl.
The arthropod that The compounds of this invention can be controlled can comprise harmful insect and pest mite.Listed specific examples below.
Hemiptera: Delphacidae, for example small brown rice planthopper (Laodelphax striatellus), brown paddy plant hopper (Nilaparvata lugens) and white backed planthopper (Sogatella furcifera); Deltocephalidae, for example rice green leafhopper (Nephotettix cincticeps) and Empoasca onukii; Aphidiadae, for example cotton aphid (Aphis gossypii) and black peach aphid (Myzus persicae); Pentatomiddae; Aleyrodidae, for example trialeurodes vaporariorum (Trialeurodes vaporariorum), tobacco aleyrodid (Bemisia tabacihe) and Bemisia argentifolii (Bemisia argentifolii); Coccidae; Tingidae; Psyllidae;
Lepidopteran: Pyralidae, for example striped rice borer (Chilo suppressalis), Cnaphalocrocis medinali(rice leaf roller) (Cnaphalocrocis medinalis), Pyrausta nubilalis (Hubern). (Ostrinia nubilalis) and Parapediasiateterrella; Noctuidae, for example prodenia litura (Spodoptera litura), beet armyworm (Spodopteraexigua), oriental armyworm (Pseudaletia separata), lopper worm (Mamestra brassicae), black cutworm (Agrotis ipsilon), Thoricoplusia spp., bollworm, Helicoverpa spp. and Earias spp.; Sulfur butterfly, for example small white (Pieris rapae crucivora); Tortricid, for example Adoxophyes orana fasciata, oriental fruit months (Grapholita molesta) and apple skin worm (Cydia pomonella); Moth fruit moth section, for example peach fruit moth (Carposina niponensis); Lyonetid section, for example apple leaf miner (Lyonetia clerkella); Gracilariidae is Phyllonorycterringoniella for example; Leaf lyonetid section is citrus leaf-miner (Phyllocnistis citrella) for example; Yponomeutidae, for example diamond-back moth (Plutela xylostella); Gelechidae, for example Pectinophora gossypiella (Pectinophoragossypiella); Arctiidae; Rain moth section;
Diptera: Calicidae is culex pipiens pollens (Culex pipiens pallens), Culex tritaeniorhynchus (Culex tritaeniorhynchus) and tropical tame mosquito (Culex quinquefasciatus) for example; Aedes (Aedes spp.) is Aedes aegypti (Aedes aegypti) and Aedes albopictus (Aedes albopictus) for example; Anopheles (Anopheles spp.) is Anopheles sinensis (Anopheles sinensis) for example; Chironomidae; Family Nuscidae, for example housefly (Musca domestica) and nonbiting stable fly (Muscina stabulans); Calliphoridae; Flesh flies; Latrine fly section; Anthomyiidae, for example delia platura (Delia platura) and onion fly (Deliaantique); Tephritidae; Drosophilidae; Hair Meng section; Tabanidae; Simulidae; Stomoxyidae; Agromyzidae;
Coleoptera: the corn root insect is corn rootworm (Diabrotica virgifera virgifera) and Diabrotica undecimpunctata howardi for example; Dung beetle section, for example Anomala cuprea and Anomala rufocuprea; Culculionidae, for example sitophilus zea-mais (Sitophilus zeamais), rice water weevil (Lissorhoptrus oryzophilus) and Callosobruchuys chienensis; TRenebrionidae, for example tenebrio molitor (Tenebrio molitor) and confused flour beetle (Tribolium castaneum); Chrysomelidae, for example rice leaf beetles (Oulema oryzae), aulacophora femoralis (Aulacophora femoralis), yellow bar leaf flea (Phyllotreta striolata) and colorado potato bug (Leptinotarsa decemlineata); Anobiidae; Epilachna spp. is ladybug of eggplant 28 stars (Epilachna vigintioctopunctata) for example; Lyctidae; Bostrichidae; Cerambycidae; Paederus fuscipes Curtis;
Total wing order: Thrips, comprise that flower thrips belongs to for example southern golden thistle horse (Thrips palmi), Frankliniella spp. is Frankliniella occidentalis (Frankliniella occidentalis) for example, and Sciltothripsspp. Sciltothrips dorsalis for example; Phlaeothripidae spp.;
Hymenoptera: Tenthredinidae; Formicidae; Vespidae;
Dictyoptera: Periplaneta (Periplaneta spp.); Blatta spp.;
Orthoptera: sword angle locust section; Gryllotalpidae;
Siphonaptera: Pulex irritans;
Anoplura: body louse;
Isoptera: Termitidae;
Acarina: Tetranychidae.
Arthropod control combination thing of the present invention comprises compound of the present invention and a kind of inert support.
Generally speaking, preparation is compound of the present invention is mixed with solid carrier, liquid vehicle, carrier gas and/or bait (base material of poison bait) etc. and to obtain, and if necessary, adds tensio-active agent and other prescription adjuvants.Preparation comprises, for example oil solution, emulsifiable concentrate, runny wettable powder, particle, dust, microcapsule etc.These preparations can transform and be used for poison bait or plate.Arthropod control combination thing of the present invention contains the The compounds of this invention of 0.01-95 weight % usually.
The solid carrier of preparation comprises, the for example fine powder of following material or particle: clay (soil, Fubasami clay, acid clay etc. take off in kaolin, diatomite, class), synthetic hydrated silicon oxide, talcum, pottery, other inorganic minerals (sericite, quartz, sulphur, activated carbon, lime carbonate etc.) or chemical fertilizer (ammonium sulfate, ammonium nitrate, ammonium chloride etc.).Liquid vehicle comprises, water for example, alcohol (methyl alcohol, ethanol, the 2-propyl alcohol, ethylene glycol etc.), ketone (acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone etc.), aromatic hydrocarbon (toluene, dimethylbenzene, ethylbenzene, methylnaphthalene etc.), aliphatic hydrocarbon (hexane, hexanaphthene, kerosene, light oil etc.), ester (ethyl acetate, butylacetate etc.), nitrile (acetonitrile, isopropyl cyanide etc.), ether (ethylene glycol dimethyl ether, Di Iso Propyl Ether, 1, the 4-diox, tetrahydrofuran (THF) etc.), acid amides (N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE etc.), halohydrocarbon (methylene dichloride, trichloroethane etc.), methyl-sulphoxide and vegetables oil (soybean oil, the cottonseed wet goods).
Carrier gas comprises, fluorocarbon for example, butagas, LPG (liquefied petroleum gas (LPG)), dme and carbonic acid gas.
Tensio-active agent comprises, alkyl sodium sulfate ester salt for example, alkylsulfonate, alkylaryl sulphonate, alkyl aryl ether, and their polyoxyethylene deriv, polyglycol ether, polyol ester and sugar alcohol derivant.
Other prescription adjuvants comprise, tackiness agent for example, dispersion agent and stablizer, specific examples such as casein, gelatin, polysaccharide (starch, Sudan Gum-arabic, derivatived cellulose, alginic acid etc.), lignin derivative, synthetic polymer (polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid etc.), PAP (iso propylbenzoic acid phosphoric acid ester), BHT (2, the 6-di-tert-butyl-4-methy phenol), BHA (the 2-tertiary butyl 4-mequinol and the 3-tertiary butyl-4-mequinol mixture), mineral oil, lipid acid and fatty acid ester.
The poison bait base material comprises, for example such as the bait composition of flour, vegetables oil, sugar and crystalline cellulose.If desired, can in poison bait, add antioxidant, for example butylated hydroxytoluene and nordihydroguaiaretic acid; Sanitas, for example dehydroacetic acid (DHA); Prevent eating by mistake agent, for example hot pepper powder; And the taste that attracts insect, for example cheesy, onion flavor and peanut oil.
The usage of arthropod control combination thing of the present invention is this arthropod control combination thing to be applied directly over insect go up and/or insect habitat (nest, planting site, soil etc.).For example when control colonizes in arthropod on the crop, arthropod control combination thing of the present invention is ejected into the crop top, is poured near the root of crop etc.
When using arthropod control combination thing of the present invention to control arthropod in agricultural and the forest, it is per 1 that consumption is generally, 000M 2Use 0.1-10, the The compounds of this invention of 000g.When arthropod control combination thing of the present invention was made into emulsifiable concentrate, runny wettable powder and microcapsule, the concentration that its usage normally is diluted with water to The compounds of this invention was 10-10,000ppm, and then spray.When arthropod control combination thing of the present invention is made into oil solution, dust and particle, normally directly use.
When using arthropod control combination thing of the present invention to control prevailing disease, consumption is generally every 1M when being used on the plane 2Use the The compounds of this invention of 0.001-100mg, the consumption in open-air place is generally every 1M 3Use the The compounds of this invention of 0.001-10mg.When arthropod control combination thing of the present invention was made into emulsifiable concentrate, runny wettable powder and microcapsule, normally at water it being diluted to The compounds of this invention concentration was 0.01-100, re-uses behind the 000ppm.When arthropod control combination thing of the present invention being made into oil solution, aerosol, smoke producing agent and poison bait, normally directly use.
Arthropod control combination thing of the present invention can also use together with other sterilants, nematocides, miticide, mycocide, weedicide, plant-growth regulator, synergistic agent, fertilizer, soil improvement agent, animal-feed etc.
Such sterilant and nematocides comprise, organo phosphorous compounds for example is as fenitrothion 95, Tiguvon, Bi Fensong, diazinon, Chlorpyrifos 94, Chlorpyrifos 94-methyl, Ortho 12420, methidathion, thiodemeton, DDVP, first Toyodan, Profenofos, cynock, dioxabenzofos, Rogor, agricultural chemicals Tsidial, Malathion, Trichlorphon, R-1582, monocrotophos, Carbicron, Nialate and lythidathion; Carbamate compounds, as BPMC, benfuracarb, Propoxur, butyl add protect hold up, SevinCarbaryl, methomyl, ethiofencarb, aldicarb, oxamyl, fenothiocarb and the two prestige of sulphur; Pyrethroid compound, as ether chrysanthemum ester, fenvalerate, esfenvalerate, Fen Puning, match rather go out, α-Sai rather goes out, ζ-Sai rather goes out, Permethrin, celo peaceful, λ-celo is peaceful, match hold up peaceful, β-Sai rather holds up, the go out peaceful, cycloprothrin, τ-taufluvalinate, protect that match is peaceful, Bi Fenning, arna rather, tralomethrin, salifluofen and halfenprox; The neonicotinoid compound is as acetamiprid, thiophene worm piperazine and thiophene worm quinoline; The benzoyloxy phenyl carbamide compound, grand as UC 62644, Teflubenzuron, flufenoxuron and Lu Fen slave; The benzoyl hydrazine compound,, chlorine hydrazides full, methoxyfenozide and ring worm hydrazides as rice; Thiadiazine derivatives, fragrant clean as cloth; The nereistoxin derivative is as Padan, thiocyclam and bensultap; The hydrochloric ether compound, as 5a,6,9,9a-hexahydro-6,9-methano-2,4, γ-BHC and 1, two (the chloro-phenyl-)-trichloro-ethyl alcohol of 1-; Carboxamidine derivatives is as Amitraz and chlordimeforin; Thiourea derivative, as eliminate Fen Nuoke; Phenylpyrazole derivatives is as ethiprole and acetoprole; Bromothalonil; Pyrrole aphid ketone; The gift promise is killed; Yin Deke; The bromo propylate; Tedion; Chinomethionate; Propargite; Fen Bu grants; It is many to close match; According to killing mite; Four mite piperazines; Bi Daben; Pyridazine; Azoles mite ester; Tebufenpyrad; Finish and eliminate sweet smell; Fenazaquin; The mite quinone goes out; Bifenazate; Fluacrypyrim; Spiral shell mite ester; Spiromesifen; The close spit of fland of going out; Avrmectin; Because of going out the spit of fland; Azadirachtin; The polynactin complex compound is as tetranactin, dinactin and trinactin; Or the like.
Below will the invention will be further described by preparation embodiment, formulation Example and test case etc.; But the present invention is not limited to these embodiment.In following preparation embodiment, 1The measurement of H-NMR data is carried out in the deuterochloroform solvent, is interior mark with tetramethylsilane.
The preparation embodiment of The compounds of this invention illustrates as follows.
Preparation embodiment 1
With 0.257g 5-chloro-3-(4-methyl-benzyl) sulphur-1,2,4-thiadiazoles and 0.145g 2,2-dimethyl-1,3-dioxolane-4-dissolve with methanol in the dinethylformamide, and adds 48mg sodium hydride (60% oil solution) at 2g N under about 0 ℃, stirred 30 minutes down at about 0 ℃ subsequently, at room temperature stirred 4 hours.Then, reaction mixture is added in the saturated sodium-chloride water solution, and extracts with t-butyl methyl ether.Concentrate organic layer, the gained resistates obtains 0.27g 5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-(4-methyl-benzyl) sulphur-1,2,4-thiadiazoles through silica gel column chromatography.5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-(4-methyl-benzyl) sulphur-1,2,4-thiadiazoles (being called compound 1 of the present invention later on)
Figure C20038010124500281
1H-NMR：7.29(d，2H) 7.11(d，2H)4.54-4.44(m，3H)4.37(d，2H)4.15-4.11(m，1H)3.83-3.80(m，1H)2.32(s，3H)1.45(s，3H)1.38(s，3H)
Preparation embodiment 2
With the following 5-chloro-3-(3 of 312mg with reference to preparation embodiment 8 preparations, the 4-dichloro benzyl) sulphur-1,2,4-thiadiazoles crude product and 0.145g 2,2-dimethyl-1,3-dioxolane-4-dissolve with methanol is at 2gN, in the dinethylformamide, and under about 0 ℃, add 48mg sodium hydride (60% oil solution), and stirred 30 minutes down at about 0 ℃ subsequently, at room temperature stirred 4 hours.Then, reaction mixture is added in the saturated sodium-chloride water solution, and extracts with t-butyl methyl ether.Concentrate organic layer, the gained resistates obtains 120mg 5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-(3, the 4-dichloro benzyl) sulphur-1,2,4-thiadiazoles through silica gel column chromatography.
5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-(3, the 4-dichloro benzyl) sulphur-1,2,4-thiadiazoles (being called compound 2 of the present invention later on)
Figure C20038010124500291
1H-NMR：7.55(s，1H)7.36(d，1H)7.26-7.22(m，1H)4.55-4.44(m，3H)4.31(s，2H)4.15-4.09(m，1H)3.84-3.80(m，1H)1.45(s，3H)1.38(s，3H)
Preparation embodiment 3
With the following 5-chloro-3-methylthio group-1 of 3.34g with reference to preparation embodiment 1 preparation, 2,4-thiadiazoles and 2.90g 2,2-dimethyl-1,3-dioxolane-4-dissolve with methanol is at 40ml N, in the dinethylformamide, and under about 0 ℃, add 880mg sodium hydride (60% oil solution), under uniform temp, stirred 1 hour subsequently.Then, reaction mixture is added in the saturated sodium-chloride water solution, and extracts with t-butyl methyl ether.The organic layer anhydrous sodium sulfate drying, the concentration residue of gained obtains 4.67g 5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-methylthio group-1,2,4-thiadiazoles through silica gel column chromatography.
5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-methylthio group-1,2,4-thiadiazoles (being called compound 3 of the present invention later on)
Figure C20038010124500301
1H-NMR：4.57-4.46(m，3H)4.16-4.09(m，1H)3.85-3.81(m，1H)2.60(s，3H)1.45(s，3H)1.35(s，3H)
Preparation embodiment 4
With following 5-chloro-3-(the 3-benzyl chloride base) sulphur-1 of 300mg with reference to preparation embodiment 6 preparations, 2,4-thiadiazoles crude product and 157mg 2,2-dimethyl-1,3-dioxolane-4-dissolve with methanol is at 2ml N, in the dinethylformamide, and add 52mg sodium hydride (60% oil solution), at room temperature stirred subsequently 2 hours.Then, reaction mixture is added in the saturated sodium-chloride water solution, and extracts with t-butyl methyl ether.The organic layer anhydrous sodium sulfate drying, the concentration residue of gained obtains 150mg 5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-(3-benzyl chloride base) sulphur-1,2,4-thiadiazoles through silica gel column chromatography.
5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-(3-benzyl chloride base) sulphur-1,2,4-thiadiazoles (being called compound 4 of the present invention later on)
1H-NMR：7.42(s，1H)7.31-7.22(m，2H)4.54-4.45(m，3H)4.35(s，2H)4.16-4.11(m，1H)3.85-3.81(m，1H)1.45(s，3H)1.38(s，3H)
Preparation embodiment 5
With following 5-chloro-3-(the 2-benzyl chloride base) sulphur-1 of 300mg with reference to preparation embodiment 5 preparations, 2,4-thiadiazoles crude product and 157mg 2,2-dimethyl-1,3-dioxolane-4-dissolve with methanol is at 2ml N, in the dinethylformamide, and add 52mg sodium hydride (60% oil solution), at room temperature stirred subsequently 2 hours.Then, reaction mixture is added in the saturated sodium-chloride water solution, and extracts with t-butyl methyl ether.The organic layer anhydrous sodium sulfate drying, the concentration residue of gained obtains 140mg 5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-(2-benzyl chloride base) sulphur-1,2,4-thiadiazoles through silica gel column chromatography.
5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-(2-benzyl chloride base) sulphur-1,2,4-thiadiazoles (being called compound 5 of the present invention later on)
1H-NMR：7.56(m，1H)7.37(m，1H)7.20(m，2H)4.56-4.45(m，5H)4.15-4.11(m，1H)3.84-3.80(m，1H)1.45(s，3H)1.38(s，3H)
Preparation embodiment 6
With following 5-chloro-3-(4-methoxybenzyl) sulphur-1 of 200mg with reference to preparation embodiment 4 preparations, 2,4-thiadiazoles and 153mg 2,2-dimethyl-1,3-dioxolane-4-dissolve with methanol in the dinethylformamide, and adds 35mg sodium hydride (60% oil solution) at 2mlN under about 0 ℃, stirred 15 minutes down at about 0 ℃ subsequently, at room temperature stirred 2 hours.Then, reaction mixture is added in the saturated sodium-chloride water solution, and extracts with t-butyl methyl ether.The organic layer anhydrous sodium sulfate drying, the concentration residue of gained obtains 200mg 5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-(4-methoxybenzyl) sulphur-1,2,4-thiadiazoles through silica gel column chromatography.
5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-(4-methoxybenzyl) sulphur-1,2,4-thiadiazoles (being called compound 6 of the present invention later on)
1H-NMR：7.33(d，2H)6.84(d，2H)4.54-4.46(m，3H)4.36(s，2H)4.15-4.13(m，1H)3.84-3.79(m，4H)1.45(s，3H)1.38(s，3H)
Preparation embodiment 7
With following 5-chloro-3-(the 4-benzyl chloride base) sulphur-1 of 416mg with reference to preparation embodiment 3 preparations, 2,4-thiadiazoles crude product and 198mg 2,2-dimethyl-1,3-dioxolane-4-dissolve with methanol is at 3mlN, in the dinethylformamide, and add down 72mg sodium hydride (60% oil solution), subsequently stir about 1 hour under uniform temp at about 0 ℃.Then, reaction mixture is added in the saturated sodium-chloride water solution, and extracts with t-butyl methyl ether.The organic layer anhydrous sodium sulfate drying, the concentration residue of gained obtains 460mg 5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-(4-benzyl chloride base) sulphur-1,2,4-thiadiazoles through silica gel column chromatography.
5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-(4-benzyl chloride base) sulphur-1,2,4-thiadiazoles (being called compound 7 of the present invention later on)
Figure C20038010124500331
1H-NMR：7.36(d，2H) 7.27(d，2H)4.55-4.44(m，2H)4.35(s，2H)4.17-4.10(m，1H)3.84-3.81(s，1H)1.47(s，3H)1.38(s，3H)
Preparation embodiment 8
With the following 5-chloro-3-benzylthio--1 of 340mg with reference to preparation embodiment 2 preparations, 2,4-thiadiazoles and 222mg 2,2-dimethyl-1,3-dioxolane-4-dissolve with methanol is at 5ml N, in the dinethylformamide, and add down 84mg sodium hydride (60% oil solution), subsequently stir about 1 hour at room temperature at about 0 ℃.Then, reaction mixture is added in the saturated sodium-chloride water solution, and extracts with t-butyl methyl ether.The organic layer anhydrous sodium sulfate drying, the concentration residue of gained obtains 370mg 5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-benzylthio--1,2,4-thiadiazoles through silica gel column chromatography.
5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-benzylthio--1,2,4-thiadiazoles (being called compound 8 of the present invention later on)
Figure C20038010124500332
1H-NMR：7.42(d，2H)7.34-7.24(m，3H)4.55-4.43(m，3H)4.40(s，2H)4.15-4.12(m，1H)3.84-3.81(m，1H)1.45(s，3H)1.35(s，3H)
Preparation embodiment 9
With the following 5-chloro-3-allyl sulfenyl-1,2 of 386mg, 4-thiadiazoles and 277mg 2 with reference to preparation embodiment 10 preparations, 2-dimethyl-1,3-dioxolane-4-dissolve with methanol in the dinethylformamide, and adds 88mg sodium hydride (60% oil solution) at 4 g N under ice-cold condition.Mixture is being added to reaction mixture in the saturated sodium-chloride water solution, and is extracting with t-butyl methyl ether after 1 hour in stirring under the ice-cold condition.The organic layer anhydrous sodium sulfate drying, the concentration residue of gained obtains 530mg 5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-allyl sulfenyl-1,2,4-thiadiazoles through silica gel column chromatography.
5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-allyl sulfenyl-1,2,4-thiadiazoles (being called compound 9 of the present invention later on)
1H-NMR：5.96(m，1H)5.32(d，1H)5.15(d，1H)4.51(m，3H)4.13(m，1H)3.84(m，3H)1.45(s，3H)1.36(s，3H)
Preparation embodiment 10
With the following 5-chloro-3-ethylmercapto group-1 of 362mg with reference to preparation embodiment 7 preparations, 2,4-thiadiazoles and 264mg 2,2-dimethyl-1,3-dioxolane-4-dissolve with methanol is at 4ml N, in the dinethylformamide, and under about 0 ℃, add 88mg sodium hydride (60% oil solution), under uniform temp, stirred 30 minutes subsequently.Then, reaction mixture is added in the saturated sodium-chloride water solution, and extracts with t-butyl methyl ether.The organic layer anhydrous sodium sulfate drying, the concentration residue of gained obtains 410mg 5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-ethylmercapto group-1,2,4-thiadiazoles through silica gel column chromatography.
5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-ethylmercapto group-1,2,4-thiadiazoles (being called compound 10 of the present invention later on)
1H-NMR：4.51(m，3H)4.14(m，1H)3.84(m，1H)3.17(q，2H)1.41(m，9H)
Preparation embodiment 11
With 0.243g 5-chloro-3-benzylthio--1,2,4-thiadiazoles and 0.098g 3-furfuralcohol are dissolved in 2g N, in the dinethylformamide, and under about 0 ℃, add 0.045g sodium hydride (60% oil solution), and stirred 1 hour down at about 0 ℃ subsequently, at room temperature stirred 2 hours.Then, reaction mixture is added in the saturated sodium-chloride water solution, and extracts with t-butyl methyl ether.Concentrate organic layer, the gained resistates obtains 0.17g 5-(3-furyl) methoxyl group-3-benzylthio--1,2,4-thiadiazoles through silica gel column chromatography.
5-(3-furyl) methoxyl group-3-benzylthio--1,2,4-thiadiazoles (being called compound 11 of the present invention later on)
Figure C20038010124500352
1H-NMR：7.56(s，1H)7.42(m，3H)7.30(m，3H)6.50(s，1H)5.37(s，2H)4.41(s，2H)
Preparation embodiment 12
With 0.334g 5-chloro-3-methylthio group-1,2,4-thiadiazoles and 0.196g 2-furfuralcohol are dissolved in 4ml N, in the dinethylformamide, and under about 0 ℃, add 0.084g sodium hydride (60% oil solution), and stirred 0.5 hour down at about 0 ℃ subsequently, at room temperature stirred 4 hours.Then, reaction mixture is added in the saturated sodium-chloride water solution, and extracts with t-butyl methyl ether.Concentrate organic layer, the gained resistates obtains 0.25g 5-(2-furyl) methoxyl group-3-methylthio group-1,2,4-thiadiazoles through silica gel column chromatography.
5-(2-furyl) methoxyl group-3-methylthio group-1,2,4-thiadiazoles (being called compound 12 of the present invention later on)
Figure C20038010124500361
1H-NMR：7.47(m，1H)6.56(m，1H)6.40(m，1H)5.45(s，2H)2.62(s，3H)
Preparation embodiment 13
Replace the 2-furfuralcohol for preparing embodiment 12 with 0.196g 3-furfuralcohol, prepare 390mg 5-(3-furyl) methoxyl group-3-methylthio group-1,2, the 4-thiadiazoles.
5-(3-furyl) methoxyl group-3-methylthio group-1,2,4-thiadiazoles (being called compound 13 of the present invention later on)
Figure C20038010124500362
1H-NMR：7.58(s，1H)7.43(d，1H)6.51(d，1H)5.38(s，2H)2.62(s，3H)
Preparation embodiment 14
Replace the 2-furfuralcohol for preparing embodiment 12 with 204mg tetrahydrochysene-3-furfuralcohol, prepare 406mg 5-(tetrahydrochysene-3-furyl) methoxyl group-3-methylthio group-1,2, the 4-thiadiazoles.
5-(tetrahydrochysene-3-furyl) methoxyl group-3-methylthio group-1,2,4-thiadiazoles (being called compound 14 of the present invention later on)
1H-NMR：4.49-4.36(m，2H)3.93-3.65(m，4H)2.84-2.74(m，1H)2.60(s，3H)2.17-2.05(m，1H)1.76-1.65(m，1H)
Preparation embodiment 15
With 835mg 3-methylthio group-5-chloro-1,2,4-thiadiazoles and 520mg Sericosol N are dissolved in 10ml N, in the dinethylformamide, and under about 0 ℃, add 204mg sodium hydride (60% oil solution), and stirred 20 minutes down at about 0 ℃ subsequently, at room temperature stirred 30 minutes.Then, reaction mixture is added in the saturated sodium-chloride water solution, and extracts with t-butyl methyl ether.With organic layer with anhydrous sodium sulfate drying after, ethyl acetate=20: 1), preparation HPLC obtains 250mg 5-(1,3-dioxolane-4-yl) methoxyl group-3-methylthio group-1 concentrate organic layer, the gained resistates is through silica gel column chromatography (hexane:, 2, the 4-thiadiazoles.
5-(1,3-dioxolane-4-yl) methoxyl group-3-methylthio group-1,2,4-thiadiazoles (being called compound 15 of the present invention later on)
Figure C20038010124500372
1H-NMR：5.08(s，1H)4.93(s，1H)4.55-4.45(m，3H)4.06-4.02(m，1H)3.82-3.78(m，1H)2.60(s，3H)
Preparation embodiment 16
With 0.334g 5-chloro-3-methylthio group-1,2,4-thiadiazoles and 228mg 2-thiophen(e)alcohol are dissolved in 4ml N, in the dinethylformamide, and under about 0 ℃, add 0.084g sodium hydride (60% oil solution), and stirred 0.5 hour down at about 0 ℃ subsequently, at room temperature stirred 4 hours.Then, reaction mixture is added in the saturated sodium-chloride water solution, and extracts with t-butyl methyl ether.Concentrate organic layer, the gained resistates obtains 66mg 5-(2-thienyl) methoxyl group-3-methylthio group-1,2,4-thiadiazoles through silica gel column chromatography.
5-(2-thienyl) methoxyl group-3-methylthio group-1,2,4-thiadiazoles (being called compound 16 of the present invention later on)
Figure C20038010124500381
1H-NMR：7.38(d，1H)7.25(d，1H)7.22(m，1H)5.65(s，2H)2.62(s，3H)
Preparation embodiment 17
With 0.334g 5-chloro-3-methylthio group-1,2,4-thiadiazoles and 228mg 3-thiophen(e)alcohol are dissolved in 4ml N, in the dinethylformamide, and under about 0 ℃, add 0.084g sodium hydride (60% oil solution), and stirred 0.5 hour down at about 0 ℃ subsequently, at room temperature stirred 4 hours.Then, reaction mixture is added in the saturated sodium-chloride water solution, and extracts with t-butyl methyl ether.Concentrate organic layer, the gained resistates obtains 500mg 5-(3-thienyl) methoxyl group-3-methylthio group-1,2,4-thiadiazoles through silica gel column chromatography.
5-(3-thienyl) methoxyl group-3-methylthio group-1,2,4-thiadiazoles (being called compound 17 of the present invention later on)
Figure C20038010124500391
1H-NMR：7.43(m，1H)7.35(m，1H)7.17(m，1H)5.49(s，2H)2.61(s，3H)
Preparation embodiment 18
(1) with 4.67g 5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-methylthio group-1,2, the 4-thiadiazoles is dissolved in the 90ml chloroform, under about 0 ℃ 3.92g 3-chlorine peroxybenzoic acid (purity 70%) is divided into aliquot and adds, and stirs subsequently.Then, reaction mixture is added in the saturated sodium sulfite aqueous solution, and uses chloroform extraction.Organic layer cleans with saturated sodium bicarbonate aqueous solution, saturated sodium-chloride water solution successively, with anhydrous sodium sulfate drying and concentrated.Resistates obtains 3.87g 5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-methylsulfinyl-1,2,4-thiadiazoles through silica gel column chromatography.
5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-methylsulfinyl-1,2, the 4-thiadiazoles
1H-NMR：4.67-4.49(m，3H)4.18-4.14(m，1H)3.86-3.32(m，1H)2.30(s，3H)1.46(s，3H)1.39(s，3H)
(2) with 2.97g 2,6-lutidine, 11.3g diacetyl oxide and 4.38g trifluoroacetic anhydride be added to 3.87g 5-(2,2-dimethyl-1; 3-dioxolane-4-yl) methoxyl group-3-methylsulfinyl-1; 2, mix down in the 4-thiadiazoles and at about 0 ℃, at room temperature placed subsequently 3 days.Then, the concentrating under reduced pressure reaction mixture is added to resistates in the saturated sodium bicarbonate aqueous solution and with t-butyl methyl ether and extracts.Concentrate organic layer, the gained resistates obtains 0.18g 5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-(acetyl-o-methyl) sulphur-1,2,4-thiadiazoles through silica gel column chromatography.
5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-(acetyl-o-methyl) sulphur-1,2,4-thiadiazoles (being called compound 18 of the present invention later on)
Figure C20038010124500401
1H-NMR：5.75(s，2H)4.57-4.47(m，3H)4.17-4.13(m，1H)3.85-3.82(m，1H)2.11(s，3H)1.45(s，3H)1.39(s，3H)
Preparation embodiment 19
(1) with 370mg 5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-benzylthio--1,2, the 4-thiadiazoles is dissolved in the 4ml chloroform, under ice-cold condition 269mg 3-chlorine peroxybenzoic acid (purity 70%) is divided into aliquot and adds, and stirs subsequently.Then, reaction mixture is added in the saturated sodium sulfite aqueous solution, and uses chloroform extraction.Organic layer cleans with saturated sodium bicarbonate aqueous solution, saturated sodium-chloride water solution successively, with anhydrous sodium sulfate drying and concentrated.Resistates obtains 360mg 5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-phenyl sulfinyl-1,2,4-thiadiazoles through silica gel column chromatography.
5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-phenyl sulfinyl-1,2, the 4-thiadiazoles
1H-NMR：7.33-7.19(m，5H)4.66-4.48(m，3H)4.42(d，1H)4.34(d，1H)4.18-4.14(m，1H)3.86-3.82(m，1H)1.47(s，3H)1.40(s，3H)
(2) 100mg sodium-acetate and 2ml diacetyl oxide are added to 80g 5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-phenyl sulfinyl-1,2, in the 4-thiadiazoles, and, refluxed subsequently 14 hours 0 ℃ of mixing down.Then, reaction mixture is added in the saturated sodium bicarbonate aqueous solution and with t-butyl methyl ether extracts.Concentrate organic layer, the gained resistates obtains 28mg through silica gel column chromatography
5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-(α-acetyl oxygen benzyl) sulphur-1,2, the 4-thiadiazoles.
5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-(α-acetyl oxygen benzyl) sulphur-1,2,4-thiadiazoles (being called compound 19 of the present invention later on)
Figure C20038010124500412
1H-NMR：7.74-7.73(m，1H)7.53-7.51(m，2H)7.41-7.35(m，3H)4.58-4.32(m，3H)4.20-4.07(m，1H)3.86-3.73(m，1H)2.10(s，3H-)1.46(s，3H)1.39(s，3H)
Preparation embodiment 20
With the following 5-chloro-3-(3 of 468mg with reference to 11 preparations of preparation example, the 5-dichloro benzyl) sulphur-1,2,4-thiadiazoles and 198mg 2,2-dimethyl-1,3-dioxolane-4-dissolve with methanol is at 3g N, in the dinethylformamide, and under about 0 ℃, add 42mg sodium hydride (60% oil solution), stirred subsequently 30 minutes.Then, add in t-butyl methyl ether and the saturated sodium-chloride water solution in reaction mixture, it is two-layer that it is divided into.Organic layer also concentrates with anhydrous sodium sulfate drying.The gained resistates obtains 72mg 5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-(3, the 5-dichloro benzyl) sulphur-1,2,4-thiadiazoles through column chromatography.
5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-(3, the 5-dichloro benzyl) sulphur-1,2,4-thiadiazoles (being called compound 20 of the present invention later on)
Figure C20038010124500421
1H-NMR：7.32(s，2H)7.24(s，1H)4.54-4.43(m，3H)4.30(s，2H)4.15-4.11(m，1H)3.84-3.81(m，1H)1.48(s，3H)1.41(s，3H)
Preparation embodiment 21
With following 5-chloro-3-(3-trifluoromethyl benzyl) sulphur-1 of 300mg with reference to 12 preparations of preparation example, 2,4-thiadiazoles and 127mg 2,2-dimethyl-1,3-dioxolane-4-dissolve with methanol in the dinethylformamide, and adds 42mg sodium hydride (60% oil solution) at 2g N under about 0 ℃, stirred 30 minutes down at about 0 ℃ subsequently, at room temperature stirred 2 hours.Then, add in t-butyl methyl ether and the saturated sodium-chloride water solution in reaction mixture, it is two-layer that it is divided into.Organic layer also concentrates with anhydrous sodium sulfate drying.The gained resistates obtains 370mg 5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-(3-trifluoromethyl benzyl) sulphur-1,2,4-thiadiazoles through column chromatography.5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-(3-trifluoromethyl benzyl) sulphur-1,2,4-thiadiazoles (being called compound 21 of the present invention later on)
1H-NMR：7.69(s，1H)7.61(d，1H)7.50(d，1H)7.42(t，1H)4.55-4.42(m，5H)4.15-4.11(m，1H)3.84-3.81(m，1H)1.45(s，3H)1.38(s，3H)
Preparation embodiment 22
With 300mg 5-chloro-3-methylamino ethoxy sulfenyl-1,2,4-thiadiazoles and 188mg 2,2-dimethyl-1,3-dioxolane-4-dissolve with methanol in the dinethylformamide, and adds 62mg sodium hydride (60% oil solution) at 3g N under about 0 ℃, stirred 30 minutes down at about 0 ℃ subsequently, at room temperature placed about 1 day.Then, add t-butyl methyl ether and saturated sodium-chloride water solution in reaction mixture, it is two-layer that it is divided into.Organic layer also concentrates with anhydrous sodium sulfate drying.The gained resistates obtains 330mg 5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-methylamino ethoxy sulfenyl-1,2,4-thiadiazoles through column chromatography.
5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-methylamino ethoxy sulfenyl-1,2,4-thiadiazoles (being called compound 22 of the present invention later on)
Figure C20038010124500441
1H-NMR：5.39(s，2H)4.58-4.47(m，3H)4.16-4.11(m，1H)3.86-3.82(m，1H)3.68-3.63(q，2H)1.45(s，3H)1.39(s，3H)1.23(t，3H)
Preparation embodiment 23
With 350mg 5-chloro-3-benzyloxy methylthio group-1,2,4-thiadiazoles and 169mg 2,2-dimethyl-1,3-dioxolane-4-dissolve with methanol is at 3g N, in the dinethylformamide, and under about 0 ℃, add 56mg sodium hydride (60% oil solution), under uniform temp, stirred 2 hours subsequently.Then, add t-butyl methyl ether and saturated sodium-chloride water solution in reaction mixture, it is two-layer that it is divided into.Organic layer also concentrates with anhydrous sodium sulfate drying.The gained resistates obtains 330mg 5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-benzyloxy methylthio group-1,2,4-thiadiazoles through column chromatography.
5-(2,2-dimethyl-1,3-dioxolane-4-yl) methoxyl group-3-benzyloxy methylthio group-1,2,4-thiadiazoles (being called compound 23 of the present invention later on)
Figure C20038010124500442
1H-NMR：7.36-7.28(m，5H)5.41(s，2H)4.69(s，2H)4.57-4.46(m，3H)4.16-4.11(m，1H)3.85-3.82(m，1H)1.45(s，3H)1.39(s，3H)
Below to describe The compounds of this invention intermediate-5-chloro-1,2, the preparation method of 4-thiadiazole compound with reference to preparation embodiment form.
With reference to preparation embodiment 1
18.7g methyl-isothiourea sulfuric ester, 25g perchloro-methyl mercaptan and 0.15 g sodium lauryl sulphate are added in the 100ml water, drip the solution of 21g dissolution of sodium hydroxide in 100ml water down above about 4 hours at about 0 ℃ subsequently.After adding, mixture was stirred 2 hours under uniform temp.Then, in reaction mixture, add t-butyl methyl ether and extracting.Concentrate organic layer.Underpressure distillation gained resistates is with after silica gel column chromatography (hexane: ethyl acetate=25: 1) obtain 7.64g3-methylthio group-5-chloro-1,2,4-thiadiazoles.
3-methylthio group-5-chloro-1,2, the 4-thiadiazoles
Figure C20038010124500451
1H-NMR：2.66(s，3H)
With reference to preparation embodiment 2
2.02g benzylisothiourea hydrochloride, 1.86g perchloro-methyl mercaptan and 46mg benzyltriethylammonium chloride are added in the mixed solution of 20ml toluene and 10ml water, drip down the 1.6g sodium hydride at about 0 ℃ subsequently and be dissolved in solution in the 10ml water, stirred 2 hours.Then, in reaction mixture, add t-butyl methyl ether and extracting.Organic layer also concentrates with anhydrous sodium sulfate drying.The gained resistates is through silica gel column chromatography (hexane: ethyl acetate=20: 1) obtain 900mg 3-benzylthio--5-chloro-1,2,4-thiadiazoles.
3-benzylthio--5-chloro-1,2, the 4-thiadiazoles
Figure C20038010124500452
1H-NMR：7.60-7.20(m，5H)4.45(s，2H)
With reference to preparation embodiment 3
10.0g 4-chlorine benzylisothiourea hydrochloride, 7.85g perchloro-methyl mercaptan and 192mg benzyltriethylammonium chloride are added in the mixed solution of 80ml toluene and 40ml water, drip the solution of 6.75g dissolution of sodium hydroxide in 40ml water down above 3 hours at about 0 ℃ subsequently.Then, in reaction mixture, add t-butyl methyl ether and extracting.Organic layer also concentrates with anhydrous sodium sulfate drying.The gained resistates obtains 5.38g 3-(4-benzyl chloride base) sulphur-5-chloro-1,2,4-thiadiazoles through silica gel column chromatography.
3-(4-benzyl chloride base) sulphur-5-chloro-1,2, the 4-thiadiazoles
Figure C20038010124500461
1H-NMR：7.37(d，2H)7.27(d，2H)4.40(s，2H)
With reference to preparation embodiment 4
2.53g 4-methoxybenzyl isothiuronium salts hydrochlorate, 2.03g perchloro-methyl mercaptan and 50mg benzyltriethylammonium chloride are added in the mixed solution of 20ml toluene and 10ml water, drip the solution of 1.74g dissolution of sodium hydroxide in 10ml water down above 4 hours at about 0 ℃ subsequently.After adding, at room temperature stirred the mixture 1 hour.Then, in reaction mixture, add t-butyl methyl ether and extracting.Organic layer also concentrates with anhydrous sodium sulfate drying.The gained resistates obtains 5.38g 3-(4-methoxybenzyl) sulphur-5-chloro-1,2,4-thiadiazoles through silica gel column chromatography.
3-(4-methoxybenzyl) sulphur-5-chloro-1,2, the 4-thiadiazoles
Figure C20038010124500462
1H-NMR：7.35(d，2H)6.85(d，2H)4.41(s，2H)3.79(s，3H)
With reference to preparation embodiment 5
10.0g 2-chlorine benzylisothiourea hydrochloride, 7.85g perchloro-methyl mercaptan and 192mg benzyltriethylammonium chloride are added in the mixed solution of 80ml toluene and 40ml water, subsequently at the solution of about 0 ℃ of following Dropwise 5 .27g dissolution of sodium hydroxide in 40ml water above 1 hour.Then, in reaction mixture, add t-butyl methyl ether and extracting.Organic layer also concentrates with anhydrous sodium sulfate drying.The gained resistates obtains 0.78g 3-(2-benzyl chloride base) sulphur-5-chloro-1,2,4-thiadiazoles through silica gel column chromatography.
3-(2-benzyl chloride base) sulphur-5-chloro-1,2, the 4-thiadiazoles
1H-NMR：7.55(d，1H)7.49(d，1H)7.22(m，2H)4.57(s，2H)
With reference to preparation embodiment 6
10.0g 3-chlorine benzylisothiourea hydrochloride, 7.85g perchloro-methyl mercaptan and 192mg benzyltriethylammonium chloride are added in the mixed solution of 80ml toluene and 40ml water, subsequently at the solution of about 0 ℃ of following Dropwise 5 .27g dissolution of sodium hydroxide in 40ml water above 1 hour.Then, in reaction mixture, add t-butyl methyl ether and extracting.Organic layer also concentrates with anhydrous sodium sulfate drying.The gained resistates obtains 1.30g 3-(3-benzyl chloride base) sulphur-5-chloro-1,2,4-thiadiazoles through silica gel column chromatography.
3-(3-benzyl chloride base) sulphur-5-chloro-1,2, the 4-thiadiazoles
Figure C20038010124500472
1H-NMR：7.43(s，1H)7.31-7.22(m，3H)4.41(s，2H)
With reference to preparation embodiment 7
10.3g ethyl isothiourea hydrobromate, 10.4g perchloro-methyl mercaptan are added in the 60ml water, slowly drip the solution of 9.39g dissolution of sodium hydroxide in 60ml water down at about 0 ℃ subsequently.Then, in reaction mixture, add t-butyl methyl ether and extracting.Organic layer also concentrates with anhydrous sodium sulfate drying.The gained resistates is through silica gel column chromatography (hexane: ethyl acetate=30: 1) obtain 2.54g 3-ethylmercapto group-5-chloro-1,2,4-thiadiazoles.
3-ethylmercapto group-5-chloro-1,2, the 4-thiadiazoles
Figure C20038010124500481
1H-NMR：3.22(q，2H)1.44(t，3H)
With reference to preparation embodiment 8
With 12.9g 3,4-dichloro benzyl isothiuronium salts hydrochlorate and 8.82g perchloro-methyl mercaptan are added in the 50ml water, slowly drip the solution of 7.58g dissolution of sodium hydroxide in 50ml water down at about 0 ℃ subsequently, stir 4 hours.Then, in reaction mixture, add t-butyl methyl ether and extracting.Organic layer also concentrates with anhydrous sodium sulfate drying.The gained resistates obtains 3.1g3-(3, the 4-dichloro benzyl) sulphur-5-chloro-1,2,4-thiadiazoles crude product through silica gel column chromatography.
3-(3, the 4-dichloro benzyl) sulphur-5-chloro-1,2, the 4-thiadiazoles
Figure C20038010124500482
With reference to preparation embodiment 9
9.46g 4-methyl-benzyl isothiuronium salts hydrochlorate and 8.11g perchloro-methyl mercaptan are added in the 50ml water, drip the solution of 6.98g dissolution of sodium hydroxide in 50ml water down at about 0 ℃ subsequently, stirred 4 hours.Then, in reaction mixture, add t-butyl methyl ether and extracting.Organic layer also concentrates with anhydrous sodium sulfate drying.The gained resistates obtains 3.6g 3-(4-methyl-benzyl) sulphur-5-chloro-1,2,4-thiadiazoles crude product through silica gel column chromatography.
3-(4-methyl-benzyl) sulphur-5-chloro-1,2, the 4-thiadiazoles
Figure C20038010124500491
With reference to preparation embodiment 10
9.33g allyl group isothiuronium salts hydrochlorate and 8.82g perchloro-methyl mercaptan are added in the 50ml water, drip the solution of 7.58g dissolution of sodium hydroxide in 50ml water down at about 0 ℃ subsequently, stirred 4 hours.Then, in reaction mixture, add t-butyl methyl ether, extract.Organic layer also concentrates with anhydrous sodium sulfate drying.The gained resistates obtains 3.6g 3-allyl sulfenyl-5-chloro-1,2,4-thiadiazoles crude product through silica gel column chromatography.
3-allyl sulfenyl-5-chloro-1,2, the 4-thiadiazoles
1H-NMR：6.03-5.83(m，1H)5.34(d，1H)5.19(d，1H)3.88(d，1H)
With reference to preparation embodiment 11
With 8.95g 3,5-dichloro benzyl isothiuronium salts hydrochlorate and 6.12g perchloro-methyl mercaptan are added in the mixed solution of 25ml water and 25ml methylene dichloride, subsequently at the solution of about 0 ℃ of following Dropwise 5 .26g dissolution of sodium hydroxide in 40ml water above about 3 hours.After adding, at room temperature stirred the mixture 1 hour.Then, adding chloroform in reaction mixture extracts.Organic layer also concentrates with anhydrous sodium sulfate drying.The gained resistates is through silica gel column chromatography (hexane: ethyl acetate=30: 1) obtain 2.4g 3-(3, the 5-dichloro benzyl) sulphur-5-chloro-1,2,4-thiadiazoles crude product.
Figure C20038010124500501
With reference to preparation embodiment 12
12.0g 3-trifluoromethyl benzyl isothiuronium salts hydrochlorate and 8.24g perchloro-methyl mercaptan are added in the mixed solution of 25ml water and 50ml methylene dichloride, drip the solution of 7.09g dissolution of sodium hydroxide in 25ml water down above about 1.5 hours at about 0 ℃ subsequently.After adding, at room temperature stirred the mixture 2 hours.Then, adding chloroform in reaction mixture extracts.Organic layer also concentrates with anhydrous sodium sulfate drying.The gained resistates is through silica gel column chromatography (hexane: ethyl acetate=20: 1) obtain 5.9g 3-(3-trifluoromethyl benzyl) sulphur-5-chloro-1,2,4-thiadiazoles.
1H-NMR：7.69(s，1H)7.61(d，1H)7.52(d，1H)7.44(t，1H)4.47(s，2H)
With reference to preparation embodiment 13
12.2g ethoxymethyl isothiuronium salts hydrochlorate and 13.2g perchloro-methyl mercaptan are added in the mixed solution of 35ml water and 70ml methylene dichloride, drip the solution of 11.4g dissolution of sodium hydroxide in 35ml water down above about 1.5 hours at about 0 ℃ subsequently.After adding, at room temperature stirred the mixture 1 hour.Then, adding chloroform in reaction mixture extracts.Organic layer also concentrates with anhydrous sodium sulfate drying.The gained resistates obtains 5.22g 3-methylamino ethoxy sulfenyl-5-chloro-1,2,4-thiadiazoles through silica gel column chromatography.
3-methylamino ethoxy sulfenyl-5-chloro-1,2, the 4-thiadiazoles
Figure C20038010124500511
1H-NMR：5.43(s，2H)3.68(q，2H)1.26(t，3H)
With reference to preparation embodiment 14
11.3g benzyloxymethyl isothiuronium salts hydrochlorate and 9.02g perchloro-methyl mercaptan are added in the mixed solution of 25ml water and 50ml methylene dichloride, drip the solution of 7.76g dissolution of sodium hydroxide in 25ml water down above about 1.5 hours at about 0 ℃ subsequently.After adding, at room temperature stirred the mixture 1 hour.Then, adding chloroform in reaction mixture extracts.Organic layer also concentrates with anhydrous sodium sulfate drying.The gained resistates obtains 3.51g 3-benzyloxy methylthio group-5-chloro-1,2,4-thiadiazoles through silica gel column chromatography.
3-benzyloxy methylthio group-5-chloro-1,2, the 4-thiadiazoles
Figure C20038010124500512
1H-NMR：7.36-7.28(m，5H)5.45(s，2H)4.69(s，2H)
Below formulation Example will be described.Umber is represented parts by weight.
Formulation Example 1
The compounds of this invention 1-23 is dissolved in 37.5 parts of dimethylbenzene and 37.5 parts of N for each each 9 parts, in the dinethylformamide, to wherein adding 10 parts of polyoxyethylene styryl phenyl ethers and 6 parts of calcium dodecylbenzene sulphonates, fully mix subsequently, obtain the emulsifiable concentrate of every kind of compound.
Formulation Example 2
The compounds of this invention 1-23 each each is added to for 9 parts contains in 4 parts of sodium lauryl sulphate, 2 parts of calcium lignin sulphonates, 20 parts of synthetic hydrated silicon oxide fine powders and the 65 parts of diatomaceous mixtures, fully stir and mix, obtain the wettable powder of every kind of compound.
Formulation Example 3
3 parts of The compounds of this invention 1-23 each each are added in 5 parts of synthetic hydrated silicon oxide fine powders, 5 parts of Sodium dodecylbenzene sulfonatees, 30 parts of bentonites and the 57 parts of clays; fully stir subsequently and mix; and in this mixture, add an amount of water; further stir; granulate and dry air with nodulizer, obtain the particle of every kind of compound.
Formulation Example 4
4.5 parts of each The compounds of this invention 1-23,1 part of synthetic hydrated silicon oxide fine powder, 1 part of DRILESS B (Sankyo CO., Ltd. makes) condensing agent and 7 parts of clays are thoroughly mixed in mortar, then with stirring juice machine stirring and evenly mixing.Add 86.5 parts of cutting clays in the gained mixture, abundant stirring and evenly mixing obtains the dust of every kind of compound.
Formulation Example 5
10 parts of The compounds of this invention 1-23 each each, 35 parts of white carbon(ink)s and 55 parts of water of containing 50 parts of Voranol EP 2001 ammonium sulfates are mixed, and pulverize, obtain the dust of every kind of compound with wet milling process.
Formulation Example 6
The compounds of this invention 1-23 is dissolved in 10 parts of methylene dichloride for each each 0.5 part, with gained solution and 89.5 parts of IsperM (isoparafin; The trade mark of Exxon Chemical) mixes, obtain the oil solution of every kind of compound.
Formulation Example 7
In each each 0.1 part of The compounds of this invention 1-23 and 49.9 parts of Noethiozol (Chuo KaseiCo. manufacturing) aerosol container of packing into.Load onto aerosol valves then, in aerosol container, charge into 25 parts of dme and 25 parts of liquefied petroleum gas (LPG), and load onto setter, obtain the aerosol of oil base.
Formulation Example 8
0.6 part, 0.01 part BHT of The compounds of this invention 1-23 each each, 5 parts of dimethylbenzene, 3.39 parts of deodorized kerosines, 1 part of emulsible reagent (Atmos 300, Atmos Chemicals Co. trade mark) and 50 parts of water are packed in the aerosol container.Load onto aerosol valves then, pressurization is packed 40 parts of propelling agents (LPG) in the aerosol container into by valve, obtains water base aerosol.
Test case shows that constantly compound of the present invention can be used as the effective constituent of arthropod control combination thing.
Test case
Each prescription dilute with water of test compounds with formulation Example 5 obtains makes the concentration of activeconstituents become 500ppm, prepares diluted liquid.
The Semen Cucumidis sativi kind in the polyethylene cup, until growing first leaf, is put about 20 cotton aphids (Aphis gossypii) and made its parasitism on leaf.After one day, the amount of above-mentioned diluent with the 20ml/ cup is sprayed on the cucumber.After using 6 days, check the quantity of cotton aphid (Aphis gossypii).
The result shows, handles through The compounds of this invention 1-9,11,13-15,17-23, and the quantity of the cotton aphid (Aphis gossypii) that lives is less than or equal to 3.And on the cucumber that does not have to handle, the quantity of the cotton aphid (Aphis gossypii) that lives is more than or equal to 20.
Industrial usability
Use The compounds of this invention can control arthropod.

Claims (4)

1, the thiadiazole compound of a kind of general formula (A):
Figure C2003801012450002C1
Wherein, in general formula (A),
R 1Represent the C1-C7 alkyl,
The C3-C7 alkenyl,
The C2-C7 alkoxyalkyl,
The C1-C2 alkyl that is replaced by phenyl, wherein phenyl randomly is selected from C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxyl group and halogen atom one or morely replaces,
The C2-C3 alkoxyalkyl that is replaced by phenyl,
The perhaps group shown in the general formula (B):
R wherein 3Represent the C1-C3 alkyl, R 4Represent hydrogen atom or phenyl;
And R 2Be the represented group of general formula (1):
Figure C2003801012450002C3
R in the formula (1) 10Represent hydrogen atom, R 11Represent the C1-C4 alkyl, X 1Represention oxygen atom or sulphur atom, m represents 1, and n represents the integer of 0-3, when n is during more than or equal to 2 integer, each R 11It is identical or different,
The represented group of general formula (2):
R in the formula (2) 10Represent hydrogen atom, R 12Represent the C1-C4 alkyl, X 1Represention oxygen atom, m represents 1, and p represents the integer of 0-7, when p is during more than or equal to 2 integer, each R 12Identical or different, perhaps
The represented group of general formula (3):
Figure C2003801012450003C2
R in the formula (3) 10Represent hydrogen atom, R 13Represent the C1-C4 alkyl, X 1Represention oxygen atom, m represents 1, and q represents the integer of 0-5, when q is during more than or equal to 2 integer, each R 13Identical or different.
2, a kind of arthropod control combination thing, it contains the thiadiazole compound of the claim 1 of significant quantity.
3, a kind of method of controlling arthropod comprises the thiadiazole compound of using the claim 1 of significant quantity to arthropod or arthropod habitat.
4, the thiadiazole compound of claim 1 is as the purposes of arthropod control combination thing.
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